WO2004080810A1

WO2004080810A1 - Portioned washing agent or detergent

Info

Publication number: WO2004080810A1
Application number: PCT/EP2004/002108
Authority: WO
Inventors: Maren Jekel; Arno DÜFFELS; Matthias Reimann; Wolfgang Barthel; Christian Nitsch; Ulrich Pegelow
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2003-03-13
Filing date: 2004-03-03
Publication date: 2004-09-23
Also published as: DE10310932B4; DE10310932A1

Abstract

The invention relates to a deep-drawing method using deep drawing molds with lowerable partial areas, preferably lowerable stamps and/or lowerable webs, which are suitable for the production of volume-optimized containers. The resulting filled containers are characterized by a low proportion of packaging.

Description

Portioned detergent or cleaning agent

The present invention is in the field of portion packaging for active substances or combinations of active substances. In particular, this invention relates to subdivided or compartmentalized packaging, that is to say packaging with a plurality of receiving chambers, for the common dosing of active substances or combinations of active substances which are incompatible with one another, and to processes for producing these packaging. A preferred field of application of the claimed agents and processes is in the field of detergents or cleaning agents, such as those used for cleaning textiles, dishes or hard surfaces.

The portioned packaging of active ingredients or combinations of active ingredients plays an important role in many areas of applied chemistry, for example in pharmacy, crop protection, but also in the area of washing or cleaning agents. The portioning avoids a possibly time-consuming and labor-intensive dosage by the user, as well as the direct contact of the user with the corresponding active ingredients.

For example, WO 93/08095 A1 (Rhone-Poulenc) discloses a bag made of water-soluble or water-dispersible material which has two receiving chambers and is suitable, for example, for packaging toxic substances. The bags can be after

Thermoforming processes are produced.

WO 02/42401 A1 (Procter & Gamble) claims a method for the automatic cleaning of dishes, which is carried out using a container with a plurality of receiving chambers. The corresponding containers have a horizontal arrangement of the individual receiving chambers and are produced by sequential adhesive bonding of individual foils to form the receiving chambers, it also being possible to use individual foils which have been shaped by deep drawing.

WO 02/85738 A1 (Reckitt Benckiser) relates to water-soluble containers with at least two receiving troughs. These containers are manufactured by gradually sealing individual foils or prefabricated individual compartments to the final container.

WO 02/85736 A1 (Reckitt Benckiser) describes water-soluble containers with at least two receiving chambers. The receiving chambers can be produced by injection molding or deep drawing, and are designed so that the closed chambers can be folded up in a mirror-image arrangement by folding. The products of the packaging processes described in the prior art, in particular the disclosed injection molding processes, are distinguished by a high proportion of packaging materials. In general, the proportion of packaging materials for deep-drawn or injection-molded packaging increases due to the material used for the partitions with the number of separate receiving chambers contained in these packaging. Since, in particular in the deep-drawing processes known from the prior art, the separation of the receiving chambers is achieved through the use of webs or stamps over which a film to be deformed is drawn, the resulting products generally have a “loss volume” that corresponds to the volume of the latter Corresponds to webs or stamps and forms the space between the separate receiving chambers. Such "loss volumes" reduce the stability of the packaged end product.

The object of the present invention was to avoid the disadvantages described above. In particular, the packaging proportion per dosing unit should be one

Multi-chamber container is reduced and the containers obtained are made more mechanically stable despite the reduced use of material. The loss volume of these containers should also be reduced.

The present application now discloses a process for packaging active substances or combinations of active substances, which is distinguished from the processes disclosed in the prior art by a reduced consumption of packaging materials, an optimized use of space in the packaging body and an increased rigidity and transport or storage stability of the resulting containers ,

It has now been found that the above-mentioned objects can be achieved if a deep-drawing process is used for packaging active ingredients, in which part of the die containing the deep-drawing troughs is lowered in the course of the process.

A first subject of this application is therefore a method for producing a container, comprising the steps of: a) deep-drawing a first wrapping material into the deep-drawing trough of a die, forming at least one receiving chamber; b) lowering a part of the die and deep drawing again, enlarging at least one of the receiving chambers formed in step a) and / or forming at least one further receiving chamber. The containers produced by the method according to the invention can be filled both after the first deep-drawing step and after the second deep-drawing step, which is carried out in connection with the lowering of part of the die, the filling of the receiving chamber after the first deep-drawing step, in particular for the Production of multi-phase fillings or compartmentalized containers (containers with separate receiving chambers) has proven to be particularly advantageous.

A preferred method according to the invention is accordingly characterized in that at least one of the receiving chambers is filled before and / or after the lowering of a part of the die.

Another preferred subject of the present application is therefore a method for producing a container, comprising the steps of: a) deep-drawing a first covering material into the deep-drawing trough of a die, forming at least one receiving chamber; b) filling at least one of the receiving chambers formed in step a); c) lowering a part of the die and deep drawing again while enlarging at least one of the receiving chamber formed in step a) and / or forming at least one further receiving chamber; d) filling at least one of the receiving chambers enlarged or formed in step c).

In a further preferred method according to the invention, at least one of the filled or unfilled receiving chambers is sealed with a second covering material before a part of the die is lowered.

Another preferred subject of the present application is therefore a method for producing a container with at least two receiving chambers, comprising the steps of: a) deep-drawing a first wrapping material into the deep-drawing trough of a die, forming at least one receiving chamber; b) filling at least one of the receiving chambers formed in step a); c) sealing at least one of the receiving chambers formed in step a) with a second wrapping material; d) lowering a part of the die and deep drawing again while enlarging at least one of the receiving chambers formed in step a) and / or forming at least one further receiving chamber; e) Filling at least one of the receiving chambers enlarged or formed in step d). In the context of the present application, “deep-drawing” or “deep-drawing methods” are methods for processing packaging materials in which, after optional pretreatment by means of heat and / or solvent, they are brought into shape by means of a suitably shaped die. The packaging material can, for example, be inserted as a plate or film between the two parts of the tool, the positive and the negative, and deformed by compressing these parts, but the deformation can also be carried out without the use of a negative tool by the action of a vacuum and / or Compressed air and / or the dead weight of the active substances or combinations of active substances included.

From the series of deep-drawing processes described, those processes are preferred in which the first wrapping material is provided in the form of a film over a die provided with depressions and is particularly preferred by the action of compressed air from the top of the films or by the action of a vacuum from the underside of the films is introduced into the recesses of the die under the simultaneous action of compressed air and vacuum and is shaped according to the shape of the recess. Particularly advantageous processes are characterized in that the film is pretreated by the action of heat and / or solvents before it is deformed. In a further preferred process variant, a film is pressed after the optional pretreatment (solvent, heat) by the action of a stamp and / or by the action of the weight of the filling material into the recess of a die.

The action of heat and / or solvents on the casing material serves to facilitate its plastic deformation. The casing material can be heated, for example, by heat radiation, hot air or, particularly preferably, by direct contact with a heating plate. Alternatively, heated rolls or rollers can also be used to heat the wrapping material. The duration of the heat treatment and the temperature of the heat radiation, hot air or hotplate surface used naturally depend on the type of the covering material used. For water-soluble or water-dispersible materials such as PVA-containing polymers or copolymers, a temperature between 90 and 130 ° C., in particular between 105 and 115 ° C., is preferred. The duration of the heat treatment, in particular the contact time when using a heating plate, is preferably between 0.1 and 7 seconds, particularly preferably between 0.2 and 6 seconds and in particular between 0.3 and 4 seconds. Contact times below one second, in particular in the range from 400 to 900 milliseconds, preferably between 500 and 800 milliseconds, have proven to be particularly advantageous for materials made from polyvinyl alcohol. There are various options for making contact between the casing material to be deformed and the heating plates. For example, the wrapping material can be guided between two mutually opposite plates, at least one of which serves as a heating plate, and brought into direct contact with the surfaces thereof by lowering and / or lifting one of these plates. Alternatively, the wrapping material can also be guided under or over a heated surface and a contact can subsequently be made by blowing the material onto the surface by means of compressed air.

If heating plates are used to heat the casing materials, the preferably film-shaped casing material can be heated uniformly over the entire surface of the film or unevenly by a so-called target heating. In a preferred embodiment of the method according to the invention, the heating takes place in a targeted manner by means of heating yards located in the heating plate.

The heating yards located in the heating plates can be planar, concave or convex. If the heating zones are convex or concave, the ratio of the maximum diameter of the heating zone to its maximum height is preferably greater than 2, particularly preferably greater than 4 and in particular greater than 8.

The target heating described above creates a grid or mesh of unheated and not very elastic film material on the film to be processed, which undesirable deformation and stretching of the film material, for example due to the weight of the film or the tensile forces acting during film transport, in the area between the heated film pieces avoids. The spatial orientation of the receiving troughs with respect to one another and the spatial orientation of the receiving troughs within the film are stabilized in this way, so that the receiving troughs are in the intended positions during further transport for filling, sealing and separating, and incorrect filling, sealing or separating is avoided.

The above-described application of a vacuum to the inside of the recesses of the die when the film is deformed has the advantage that the air located in the recess below the deforming envelope material can be removed in a simple manner and the deformed envelope material can be kept in the deformed state. Preferred continuous deep-drawing processes, that is to say processes on a continuous endless die, in which the receiving chambers produced by deformation remain in the depressions of the die until they are filled or sealed or even cut out, are distinguished by the fact that the receiving containers formed in the depressions are characterized by a vacuum which is applied during the shaping process and until the end of the filling process, preferably until at the end of sealing, particularly preferably until the container is cut out of the foil grid, are kept in their deformed state. In the case of discontinuous processes, that is to say processes in which the film transport is interrupted periodically and the deformed covering material is removed from the recesses of the matrices and filled into a filling station before filling, it is preferred for the preformed containers in the filling station to be in the same manner with the die recesses identical or spatially similar loading forms are placed, in which a vacuum is applied before and / or during and / or after filling in order to keep the preformed receiving chambers in their shape and to prevent, for example, shrinkage and / or wrinkling. The vacuum should be selected in such a way that the receiving chambers formed from the flat foils are kept in their shape, the corresponding covering material is not damaged by the action of the vacuum and spillage of the active ingredient (s) after filling in the receiving chambers is avoided by shrinking the receiving chamber. The exact value for the vacuum depends, among other things, on the type of envelope material used or its wall thickness. Typically, however, a vacuum is in the range from 0.01 to 1 bar, preferably between 0.1 and 0.8 bar, particularly preferably between 0.2 and 0.6 bar.

The receiving chambers formed by deep drawing can have any technically feasible shape. Spherical-dome-shaped, cylindrical or cubic chambers are particularly preferred. Preferred receiving chambers have at least one edge and one corner, receiving chambers with two, three, four, five, six, seven, eight nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more edges or two, three, four, five, six, seven, eight nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more corners are also feasible and preferred according to the invention. Further feasible and preferred in alternative embodiments of the inventive method receiving chambers have a dome-shaped structure. The side walls of the receiving chambers are preferably planar. Spatially opposite side walls can be arranged both parallel and not parallel to one another. The base area of the receiving chambers can be convex, concave or planar, with planar base areas being preferred. The base area itself can be designed as a circle, but can also have corners. Base areas with a corner (teardrop shape), two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more corners are in Preferred within the scope of the present application. In preferred embodiments of this application, the transition from the base area to the side wall (s) or the transition of the side walls into one another is designed in a rounded form. The receiving chambers therefore have no pointed or sharp, but rather rounded edges. A preferred method according to the invention is therefore characterized in that the base areas of the receiving chambers are planar.

The dimensions and the volume of the receiving chambers and spaces formed by the shaping processing will primarily be based on the later application of the resulting containers. In a preferred variant of the method according to the invention, the receiving chambers become a total volume between 0.1 and 1000 ml, preferably between 0.2 and 100 ml, particularly preferably between 0.4 and 50 ml, very particularly preferably between 0.6 and 30 mL and especially between 0.8 and 10 mL deep-drawn. In the context of the method according to the invention, it is desirable in a preferred embodiment that the at least two receiving chambers have the same spatial shape and an identical volume. In another preferred embodiment, the at least two receiving chambers present in the container have different volumes, the ratio of these volumes preferably being between 25: 1 and 1.05: 1, preferably between 20: 1 and 2: 1 and in particular between 15: 1 and 4: 1. In preferred methods according to the invention, the container has two receiving chambers of different volumes, the volume of the smaller receiving chamber being at least 2%, preferably at least 5%, particularly preferably at least 10% and in particular at least 20%, 30%, 40%, 50%, 60% , 65%, 70%, 75% or 80% of the volume of the larger receiving chamber. The volume of the individual chambers is preferably between 0.05 and 900 ml, particularly preferably between 0.1 and 90 ml, very particularly preferably between 0.5 and 40 ml and in particular between 1.0 and 25 ml.

In a preferred embodiment of the method according to the invention, the containers have receiving chambers with different depths. There is not necessarily a direct connection with the chamber depth and the chamber volume. For example, in a container with two receiving chambers, the receiving chamber with the smaller chamber depth can certainly have the larger chamber volume, while the receiving chamber with the greater chamber depth has a smaller volume. The two or more chambers can also have the same volume despite different chamber depths. However, in the context of the present application, a method is preferred in which the receiving chamber with the smaller chamber depth also has a smaller volume in comparison with the other receiving chamber (s), with reference to the above in terms of the absolute volumes and the volume ratios Information is referenced. Containers produced according to a preferred method according to the invention have receiving chambers with vertically sloping side walls. However, containers in which at least one receiving chamber has an inclined side wall are particularly preferred. In such receiving chambers, the angle between the side wall and an imaginary seal closing the receiving chamber is therefore less than 90 °. Of course, this angle can vary for the different side walls of a single receiving chamber. If the receiving chamber has only a single side wall (cylinder-like receiving chambers), even a single side wall can have different angles with the corresponding shaping of the deep-drawing troughs used in deep-drawing. Preference is given to receiving chambers in which the said angle is 30 and 90 °, preferably between 35 and 89 °, particularly preferably between 40 and 88 ° and in particular between 45 and 87 °.

The receiving chambers produced by the shaping processing can also have gradations. The corresponding receiving chambers produced in a preferred method variant accordingly have no flat side walls, but rather have side walls which are characterized by steps or curvatures. The number of curvatures can vary, methods being preferred in which the number of steps and / or curvatures in one or more receiving chambers per chamber is at most 10, preferably between 1 and 9, particularly preferably between 1 and 8, entirely is particularly preferably between 2 and 7 and in particular between 2 and 6. The steps or curvatures can be circumferential in the respective receiving troughs or only on individual side walls. The course of the steps or curvatures is preferably horizontal. Steps and / or curvatures with an upward or downward course similar to a screw thread can, however, also be realized and are preferred for certain fields of application.

In the context of this application, the “volume” of the receiving chambers refers to the filling volume that can be achieved by filling the chambers or spaces with a liquid without overflowing this liquid onto the preferably planar sealing edges. The receiving chamber (s) produced by the deep-drawing process can / can If more than one chamber is formed in step a) of the process according to the invention, the filling of these two, three, four, five or more chambers can take place simultaneously or at different times not to fill two, three or four of the receiving chambers created in step a) before sealing, the resulting packaging then being characterized by increased buoyancy when used in liquid, preferably aqueous media. After filling, the filled receiving chambers can be sealed with another covering material. The sealing is preferably carried out by the action of pressure and / or heat and / or solvent. The further wrapping material used for sealing can be identical to the wrapping material used in step a) of the method according to the invention, but can also differ from it both in its composition or in its thickness.

In a preferred embodiment of the method according to the invention, the surface of the wrapping material is first dissolved by solvent before sealing (in the case of water-soluble films, water is particularly suitable here) and then sealed by the action of pressure and / or heat. Suitable sealing temperatures for water-soluble casing materials are, for example, 120 to 200 ° C., preferably temperatures in the range from 130 to 170 ° C., in particular in the range from 140 to 150 ° C. Pressures in the range from 250 to 800 kPa, preferably 272 to 554 kPa, particularly preferably from 341 to 481 kPa have proven to be advantageous as the sealing pressure. The sealing times are preferably at least 0.3 seconds, preferably between 0.4 and 4 seconds. Sealing temperatures, pressure and sealing times are determined not only by the wrapping material used but also by the sealing machine used. In a preferred method according to the invention, the sealing seams have a width between 0.5 and 7 mm, preferably between 1.0 and 6 mm and in particular between 1.5 and 5 mm. Sealing seams with a width above 2 mm, preferably above 2.5 mm, particularly preferably above 3 mm and in particular above 3.5 mm have proven to be sufficiently durable. Since the width of the seal number can vary depending on the production, even for a single package, the above-mentioned information about the width of the seal seam relates to the minimum number of channels measured for an individual package. Sealing takes place in particular when the contents are liquid or flowable. Examples of such filling goods are liquids, gels or particulate solids such as powder.

The sealing of the receiving chambers not only avoids contact of the filled active substances with each other or with the surrounding atmosphere (e.g. atmospheric oxygen, atmospheric humidity) or skin contact with the consumer, the sealing also enables the choice of suitable sealing materials control the release of the active ingredients located within the sealed cavity. An example of such a control is the use of water-soluble or water-dispersible sealing and / or wrapping materials with different solubilities with the aim of releasing the contents of individual receiving chambers into the surrounding aqueous medium in a chronologically defined order. In the context of the present application, methods can be implemented in which the envelope materials used to seal the receiving chambers are the same or different materials. In - Kl ¬

In a preferred embodiment, the same wrapping materials are used for sealing the receiving chambers. This embodiment enables the contents to be released under the sealing surfaces at the same time. In a further preferred embodiment, the materials used for sealing the receiving chambers differ.

It is characteristic of the method according to the invention that part of the die is lowered. In the context of the present application, it is preferred to lower a web or punch located in the deep-drawing trough of the die and / or a part of the die at least partially surrounding the deep-drawing trough in step a).

Within the scope of the present application, stamps are those movable tools within the deep-drawing recess of the die which have no contact with the side walls of the deep-drawing recess. The minimum distance of the stamp from the side walls of the deep-drawing trough is sufficient to ensure deep-drawing of the films used in step a) between the stamp and the side wall. This distance is preferably at least 3 mm, preferably at least 5 mm, particularly preferably between 8 and 120 mm, very particularly preferably between 10 and 90 mm and in particular between 12 and 70 mm.

Within the scope of the present application, the term web is used to denote such movable tools within the deep-drawing recess of the die which have at least one contact area with one of the side walls of the deep-drawing recess, in which deep-drawing of a film between the web and the side wall is not possible. The distance between the web and the side wall in this contact area is preferably less than 1000 / m, preferably less than 500 m, particularly preferably less than 400 μm and in particular less than 300 μm.

In the context of the present inventions, in particular those methods are preferred in which the web or stamp is lowered to less than 95%, preferably less than 80%, particularly preferably to less than 65% and in particular less than 50% of its original height. The original height of the web or stamp is the height of the section of the web or stamp that protrudes from the bottom surface of the deep-drawing trough of the die and over which the first covering material was drawn in step a) of the method according to the invention. At the beginning of the process in step a), the tip of the web or stamp, or the upper part of the web or stamp, can both protrude beyond the plane formed by the die surface and also be in register with this plane, but also below this plane are located. All three process variants are preferred in the context of the present application. In a preferred embodiment of the method according to the invention, the web or stamp is lowered in step d) to a height between 5 and 95%, preferably between 10 and 855, particularly preferably between 15 and 75% and in particular between 20 and 65% of its original height.

The web or stamp preferably have a maximum width between 0.5 and 50 mm, preferably between 0.6 and 40 mm, particularly preferably between 0.7 and 30 mm and in particular between 0.8 and 20 mm.

In addition to a web or a punch, one or more part (s) of the die surrounding the deep-drawing trough can also be lowered in the method according to the invention, these preferably completely surrounding the deep-drawing trough, for example in the form of a ring. Also preferred are methods according to the invention in which the entire deep-drawing trough located in the die, including a part of the die surrounding this deep-drawing trough, is lowered.

By lowering part of the die in the method according to the invention, the volume of the deep-drawing trough is increased by the volume of the lowered tool. This increase in volume in methods preferred according to the invention is between 0.5 and 40 ml, preferably between 0.7 and 25 ml, preferably between 0.8 and 20 ml, particularly preferably between 0.9 and 16 ml and in particular between 1.0 and 13 ml.

The ratio of the volume of the deep-drawing trough before lowering the tool to the volume of the deep-drawing trough after lowering the tool is preferably between 1:40 and 40: 1, preferably between 1:38 and 38: 1 and in particular between 1:32 and 32: 1 ,

In a preferred embodiment of the method according to the invention, the container or at least one receiving chamber of the container is sealed with a third covering material after the tool has been lowered. This third wrapping material can be identical to or different from the first and / or the second wrapping material.

In a further preferred embodiment of the method according to the invention, the container or at least one receiving chamber of the container is sealed with a third wrapping material after the tool has been lowered and after at least one of the receiving chambers formed or enlarged by the lowering has been filled. This third wrapping material can be identical to or different from the first and / or the second wrapping material. Before, at the same time as or after this last sealing step, the containers produced in the method according to the invention are preferably separated by the action of knives or punches to form a brim extending around the top of the container. The width of this brim, in addition to other parameters, also depends on the choice of the deep-drawing process used to produce the corresponding containers. In these methods, two variants can be distinguished, among others, all of which are particularly preferred for carrying out the method according to the invention. These are processes in which the wrapping material is guided horizontally into a molding station and from there in a horizontal manner for filling and / or sealing and / or singling, again differentiating between continuous and discontinuous processes, and processes in which the Wrapping material is guided over a continuously rotating forming roller. When carrying out continuous processes in which the deformed casing material remains in the deep-drawing trough after deep-drawing for filling and / or sealing and / or separating, smaller brim widths in the range from 1 to 4 mm tend to be achievable, while in the case of discontinuous processes the brim widths tend to be in the range from 2.5 to 5 mm.

In general, all envelope materials that can be processed by deep-drawing methods can be used in the method according to the invention, although the use of water-soluble or water-dispersible packaging materials is preferred. Preferred processes according to the invention are accordingly characterized in that at least one of the casing materials used is water-soluble or water-dispersible, with in a particularly preferred embodiment of the process according to the invention at least two of the casing materials used, preferably the first and the second or the first and the third, with regard to their Distinguish resolution properties.

Some particularly preferred water-soluble or water-dispersible coating materials which are suitable both for producing the receiving chambers and for sealing them are listed below. The polymers mentioned can be used as a sealing material or shell material either alone or in combination with one another or in combination with other substances, for example plasticizers or solubilizers.

a) water-soluble nonionic polymers from the group of a1) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the group of b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers bδ) alkyl acrylamide / methyl methacrylic acid (meth) acrylic acid

Copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate

Copolymers bδ) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of d) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyllrialkylammonium chloride / methacrylic acid copolymers and their

Alkali and ammonium salts c3) methacroylethyl betaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of d1) vinyl acylate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid or Mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the non-ionic type, dδii) at least one monomer of the ionic type, dδiii) of polyethylene glycol and dδiv) a crosslinker d6) by copolymerization of at least one monomer of each of the following three

Copolymers obtained in groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, dθiii) esters of long-chain carboxylic acids and unsaturated alcohols and / or

Esters of the carboxylic acids of group dδii) with saturated or unsaturated, linear or branched C ₈ ι ₈ alcohol d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra- and pentapolymers of dδii D8i) crotonic acid or allyloxyacetic) Vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters dδiv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the group

Ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts d10) Terpolymers from vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the D-position

e) water-soluble cationic polymers from the group of e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and

Amides of acrylic acid and methacrylic acid e5) copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate e6) vinyl pyrrolidone methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol eδ) under the INCI names Polyquaternium 2, polyquaternium 2, polyquaternium 2

Polyquaternium 18 and Polyquaternium 27 indicated polymers.

Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.

The wrapping material used in the process according to the invention is preferably at least partially a substance from the group (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin.

In a preferred process variant, the container comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof. "Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

which in small proportions (approx. 2%) also structural units of the type

- CH2 - CH - CH CH2

OH OH

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-δ9 mol%. , therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

In the context of the present invention, it is preferred that the shell material used in the process according to the invention at least partially comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular Is 82 to δδ mol%. In a preferred embodiment, the first envelope material used in the method according to the invention consists of at least 20 wt .-%, particularly preferably at least 40 wt .-%, very particularly preferably at least 60 wt .-% and in particular at least δO wt .-% of a polyvinyl alcohol, the degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to δ9 mol% and in particular δ2 to δδ mol%.

Polyvinyl alcohols of a specific molecular weight range are preferably used as materials for the containers, it being preferred according to the invention that the shell material comprises a polyvinyl alcohol, the molecular weight of which ranges from 10,000 to 100,000 gmol ^"1 , preferably from 11,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 up to 80,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^{" 1} .

The degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1600.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^{® 4-8δ,} Mowiol ^{® δ-δ8} and Mowiol ^{® δδ} 8.

Further polyvinyl alcohols that are particularly suitable as wrapping material can be found in the table below:

Other polyvinyl alcohols suitable as wrapping material are ELVANOL 51-05, 52-22, 50-42, 85-δ2, 7δ-1 δ, T-2δ, T-66, 90-δO (trademark of Du Pont), ALCOTEX ^® 72. δ, 7δ, B72, FδO / 40, F88 / 4, F88 / 26, F8δ / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-Oδ, A-300, AH-22, C- δOO, GH-20, GL-03, GM-14L, KA-20, KA-δOO, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK) , The water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water. The reaction products made of PVAL and starch are extremely advantageous to use.

Furthermore, the solubility in water can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values. Films made of PVAL are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Examples of suitable water-soluble PVAL films are the PVAL films available from Syntana Handelsgesellschaft E. Harke GmbH & Co. under the name "SOLUBLON ^® ". Their solubility in water can be adjusted to the degree, and films of this product range are available which are soluble in the aqueous phase in all temperature ranges relevant to the application.

Polyvinylpyrrolidones, abbreviated as PVP, can be described by the following general formula:

PVPs are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range from approx. 2,600 to 760,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H- [0-CH ₂ -CH ₂ ] _n -OH

which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range from approx. 200 to δ,000,000 g / mol, corresponding to polymer degrees n from approx. δ to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: approx. 16,000 to> 2δ0,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

Within the scope of the method according to the invention, preference is given to enveloping materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.

Starch is a homoglycan, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight chain amylose (MW. Approx. 50,000 to 150,000) and 70 to δ0% branched chain amylopectin (MW. Approx. 300,000 to 2,000,000). There are also small amounts of lipids,

Contain phosphoric acid and cations. While the amylose forms 1, 4-position long, helical, intertwined chains with about 300 to 1,200 glucose molecules as a result of the bond, the chain in the amylopeklin branches to an ast-like one after 1,6 ch bonded by an average of 25 glucose units Formations with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch derivatives which are obtainable by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.

Pure cellulose has the formal gross composition (C ₆ Hιo0 ₅ ) _n and formally considered a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000. As Cellulose-based disintegrants can also be used in the context of the present invention, cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

Preferred methods according to the invention are characterized in that at least one of the envelope materials used is transparent or translucent.

The wrapping material used, for example, for deep drawing and / or sealing is preferably transparent. For the purposes of this invention, transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%. As soon as a wavelength of the visible spectrum of light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.

Containers produced according to the invention, for the manufacture of which transparent envelope material was used, can contain a stabilizing agent. Stabilizing agents within the meaning of the invention are materials which protect the ingredients located in the receiving chambers from decomposition or deactivation by exposure to light. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. In order to prevent undesired changes to the formulations caused by light radiation and thus radical decomposition, the formulations can contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other classes of substances are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives, such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate, organosulfur blends, such as the esters of 3,3'-thiodipropionic acid with C _1-18 alkanols, in particular Cι _0-18 alkanols, metal ion deactivators, which are able to complex the autooxidation catalyzing metal ions, such as copper, such as nitrilotriacetic acid and their descendants and their mixtures. Antioxidants can be present in the formulations in amounts of up to 3δ% by weight, preferably up to 2δ% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.

Another class of stabilizers that can preferably be used are the UV absorbers. UV absorbers can improve the lightfastness of the recipe components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. In addition, substituted benzotriazoles, such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) - 4-hydroxy-δ- (methylpro-pyl) monosodium salt (Ciba Fast ^® H), 3-phenyl-substituted acrylates ( Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylals, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid. Of particular importance are biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 4-

2-ethylhexyl (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably 4-methoxybenzmalonic acid di-2-ethylhexyl ester; Triazine derivatives, such as, for example, 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3, δ-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione; Ketotricyclo (δ.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3- bornylidenemethyl) benzene-sulfonic acid and 2-methyl-δ- (2-oxo-3-bomylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1 - (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-meth-oxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1, 3-dione and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between δ and 60 nm and in particular between 16 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape. The pigments can also be surface treated, i.e. are hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 806 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.

UV absorbers can be used in amounts of up to δ% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight, in each case based on the total weight of a substance mixture located in a receiving chamber.

Another class of stabilizers to be used with preference are the fluorescent dyes. They include the ^{^{4,4'-diamino-2,2'-stilbenedisulfonic}} acids (flavonic), 4,4'-distyrylbiphenyls, methyl umbelliferone, coumarins, dihydroquinolinones, 1, 3- diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole, and Benzimidazole systems and the pyrene derivatives substituted by heterocycles. The sulfonic acid salts of the diaminostilbene derivatives and polymeric fluorescent substances are of particular importance. Fluorescent substances, based on the total weight of a substance mixture located in a receiving chamber, in amounts of up to δ% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0, δ and in particular from 0.03 to 0 , 1 wt .-% be included.

In a preferred embodiment, the aforementioned stabilizing agents are used in any mixtures. The stabilizing agents are, based on the total weight of a substance mixture located in a receiving chamber, in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 up to δ% by weight.

In a preferred method according to the invention, at least one of the shell material (s) used consists of a water-soluble or water-dispersible polymer, preferably a polymer film.

Preferred process variants are characterized in that the film used in step a) of the process according to the invention has a thickness of δ to 2000 m, preferably from 10 to 1000 μm, particularly preferably from 15 to 500 μm, very particularly preferably from 20 to 200 μm and in particular from 25 to 100 // m.

The foils used can be single or multi-layer foils (laminate foils). The water content of the films is preferably below 10% by weight, particularly preferably below 7% by weight, very particularly preferably below 5% by weight and in particular below 4% by weight.

As can be seen from the above information, the agents produced according to the invention are particularly suitable for the controlled release of the active substances contained, in particular the active substances from the group of washing or cleaning agents.

According to the invention, preference is accordingly given to an embodiment in which the container as a whole is water-soluble, that is to say it dissolves completely when used as intended for washing or machine cleaning when the conditions provided for the dissolution have been reached. A significant advantage of this embodiment is that the container can be at least partially detached in the cleaning liquor within a practically relevant short time - as a non-limiting example, a few seconds to δ min - under precisely defined conditions, and thus, according to the requirements, the encapsulated content, ie. h, brings the cleaning-active material or several materials into the fleet. This release can only be controlled or controlled in different ways. In a first embodiment of the invention, which is particularly preferred on account of advantageous properties, the water-soluble container comprises areas which are less or not water-soluble at all or areas which are water-soluble only at higher temperatures and areas which are water-soluble or water-soluble at low temperatures. In other words, the container does not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only at a changed electrolyte concentration the desired value achieved, on the other hand. This can lead to certain areas of the container becoming detached when used as intended under adjustable conditions, while other areas remain intact. A container with pores or holes is formed, into which water and / or liquor penetrate, detach active, rinse-active or cleaning-active ingredients and can be discharged from the container. Systems in the form of multi-chamber containers or in the form of containers arranged one inside the other (“onion system”) can also be provided in the same way. In this way, systems with controlled release of the wash-active, rinse-active or cleaning-active ingredients can be manufactured.

The invention is not subject to any restrictions on the formation of such systems. Thus, containers can be made in which a unitary polymer material comprises small areas of incorporated compounds (e.g. salts) which are more water soluble than the polymer material. On the other hand, several polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble.

It corresponds to a particularly preferred embodiment of the invention that the less readily water-soluble areas or not at all water-soluble areas or only at higher temperatures water-soluble areas of the containers are areas made of a material which chemically essentially corresponds to that of the readily water-soluble areas or at lower temperatures water-soluble areas corresponds, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in the case of PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or a content of a water-insoluble polymer. Even considering the fact that the containers do not completely dissolve, so portioned detergent or cleaning agent compositions according to the invention can be provided which have advantageous properties in the release of active substances, in particular active substances from the group of detergents or cleaning agents, into the respective liquor.

In addition to this controlled release through the targeted choice of the shell materials used, the person skilled in the art has other methods available. An alternative procedure, which is suitable for the controlled release of active substances or active substance mixtures alone or in combination with the above-mentioned control by selecting certain coating materials, is the integration of one or more "switches" in the above-mentioned active substances, active substance mixtures or active substance preparations.

Possible "switches" that influence the dissolution behavior of the active substances enclosed in the containers according to the invention are, in particularly preferred embodiments, physicochemical parameters. Examples include, but should not be construed as a limitation

the mechanical stability, for example of a capsule, a coating or a compacted shaped body such as a tablet, which - depending on the time of the

Temperature or other parameters - can be a factor determining disintegration; the soluble wedge of optionally used capsules or coatings or matrices in

Dependence on pH and / or temperature and / or ionic strength; the dissolution rate of optionally used capsules or coatings or

Matrices as a function of pH and / or temperature and / or ionic strength; the melting behavior (the melting point) of optionally used capsules or

Coatings or matrices depending on pH and / or temperature and / or ionic strength;

In a particularly preferred embodiment, the agent produced according to the invention comprises at least one active substance or active substance preparation, the release of which is delayed. The delayed release is preferably delayed by the use of at least one of the agents described above, but in particular by the use of different packaging materials and / or the use of selected coating materials, it being particularly preferred that this delayed release occurs when active substances or mixtures of active substances are used the group of washing or cleaning agents at the earliest δ minutes, preferably at the earliest 7 minutes, particularly preferably at the earliest 10 minutes, very particularly preferably at the earliest 1δ minutes and in particular at the earliest 20 minutes after the start of the cleaning or washing process. The use of meltable coating materials from the group of waxes or paraffins is particularly preferred.

A method which is particularly preferred according to the invention is characterized in that the resulting container has at least two receiving chambers which are filled with different means in each case. The agents can differ in their composition, as well as in their composition and state of matter. In the following, a distinction is made with respect to the physical states of the fillable active substances or combinations of active substances between solid and liquid agents, whereby as solid substances within the scope of the present application active substances and active substance combinations are summarized which have a solid, that is to say dimensionally stable, non-flowable consistency. This category includes, for example, substances in the solid state, but also dimensionally stable substances such as dimensionally stable gels and combinations of these substances. Filled bodies with a solid outer shell are also referred to as solids, regardless of the physical state of the fillers contained in these filled bodies.

In the context of the present application, solids are preferably powders and / or granules and / or extrudates and / or compactals and / or castings, regardless of whether they are pure substances or mixtures of substances. The solids mentioned can be in amorphous and / or crystalline and / or partially crystalline form.

In the context of the present invention, preferred solids have a water content (for example, determinable as a loss on drying or according to Karl Fischer) below 7% by weight, preferably below 4.δ% by weight, and particularly preferably below 2% by weight.

Powder is a general term for a form of separation of solid substances and / or mixtures of substances which is obtained by comminution, i.e. grinding or crushing in the grinding bowl (pulverization), grinding in mills or as a result of atomization or freeze drying. A particularly fine division is often called atomization or micronization; the corresponding powders are called micro powders. Preferred powders have a uniform (homogeneous) mixture of the solid, finely divided constituents and, in the case of substance mixtures, in particular do not tend to be separated into individual constituents of these mixtures. Powders which are particularly preferred in the context of the present application therefore have a particle size distribution in which at least 80% by weight, preferably at least 60% by weight, particularly preferably at least 9δ% by weight and in particular at least 99% by weight of the powder, in each case based on its total weight, deviate from the mean particle size of this powder by a maximum of 80%, preferably a maximum of 60% and in particular a maximum of 40%. According to the grain size, the powders are roughly divided into coarse, fine and. Very fine powder common; A more precise classification of powdered bulk goods is based on their bulk density and by sieve analysis. In principle, powders of any particle size can be used, but preferred powders have average particle sizes from 40 to δOO μm, preferably from 60 to 400 μm and in particular from 100 to 300 μm. Methods for determining the average particle size are usually based on the aforementioned sieve analysis and are described in detail in the prior art.

The unwanted caking of the powders can be countered by using pouring aids or powdering agents. In a preferred embodiment, the powders produced in the process according to the invention therefore contain free-flowing aids or powdering agents, preferably in parts by weight of 0.1 to 4% by weight, particularly preferably of 0.2 to 3% by weight and in particular of 0 , 3 to 2 wt .-%, each based on the total weight of the powder. Preferred pouring aids or powdering agents are, preferably in finely ground form, silicates and / or silicon oxide and / or urea.

As a particulate mixture, powders can be agglomerated using a number of techniques. Any method known in the prior art for agglomeration of particulate mixtures is in principle suitable for converting the solids enclosed in the containers produced according to the invention into larger aggregates. In the context of the present invention, agglomerates which are preferably used as solid (s) are the compactals and extrudals in addition to the granules.

Accumulations of granules are referred to as granules. A granulate is an asymmetrical aggregate of powder particles. Granulation processes are widely described in the prior art. Granules can be produced by wet granulation, by dry granulation or compacting and by melt solidification granulation.

The most common granulation technique is wet granulation, since this technique is subject to the fewest restrictions and is the safest way to produce granules with favorable properties. Moist granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably carried out in mixers, fluidized beds or spray towers, it being possible for said mixers to be equipped, for example, with stirring and kneading tools. However, combinations of fluidized bed (s) and mixer (s) or combinations of different mixers can also be used for the granulation. The granulation takes place depending on the starting material and the desired product properties under the influence of low to high shear forces.

If the granulation takes place in a spray tower, the starting materials used can be, for example, melts (melt solidification) or, preferably aqueous, slurries (spray drying) solid substances which are sprayed at the top of a tower in a defined droplet size, freeze or dry in free fall, and on Bottom of the tower accumulate as granules. Melt solidification is generally particularly suitable for shaping low-melting substances that are stable in the melting temperature range (e.g. urea, ammonium nitrate and various formulations such as enzyme concentrates, pharmaceuticals, etc.), the corresponding granules are also referred to as prills. Spray drying is used particularly for the production of detergents or detergent components.

Further agglomeration techniques described in the prior art are extruder or perforated roller granulation, in which powder mixtures optionally mixed with granulating liquid are plastically deformed when pressed by perforated disks (extrusion) or on perforated rollers. The products of extruder granulation are also called extrudates.

Compactates can be produced, for example, using dry granulation techniques such as tableting or roller compaction. Compacting in tablet presses enables single-phase or multi-phase tablets or briquettes to be produced. In addition to the multi-layer or sandwich tablets, the multi-phase tablets also include, for example, the coated tablets and the point tablets (bull-eye tablets). The briquettes, like the slugs produced in compacting rollers, can be comminuted after the compacting by counter-rotating spiked rollers or beaten by sieves.

In the context of the present application, casting bodies are solid substance particles which are produced by solidification and / or crystallization from melts or solutions. The solidification and / or crystallization preferably takes place in prefabricated matrices. Depending on the size of the die and the intended use of the casting body, the casting bodies released from the dies after solidification can subsequently be used in their original size or, if appropriate, after comminution, as solids in the water-soluble containers according to the invention.

Fusible substances are particularly suitable as matrix material for the abovementioned solids, but in particular for castings which are produced by melt solidification from the group of fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or waxes and / or parrafins.

Fat (s) or triglyceride (s) is the name for compounds of glycerol in which the three hydroxyl groups of the glycerol are esterified by carboxylic acids. The naturally occurring fats are triglycerides, which usually contain different fatty acids in the same glycerin molecule. By saponification of the fats and subsequent esterification or reaction with acyl chlorides, synthetic triglycerides in which only one fatty acid is bound are also accessible (e.g. tripalmitin, triolein or tristearin). Natural and / or synthetic fats and / or mixtures of the two are preferred as matrix material or matrix component for castings or one of the other solids mentioned in the context of the present invention.

Aliphatic saturated or unsaturated, carboxylic acids with branched or unbranched carbon chain are referred to as fatty acids in the present application. A large number of production methods exist for the production of the fatty acids. While the lower fatty acids are mostly based on oxidative processes based on alcohols and / or aldehydes as well as aliphatic or acyclic hydrocarbons, the higher homologues are mostly still most easily accessible today by saponification of natural fats. Advances in the field of transgenic plants mean that there are almost unlimited possibilities for varying the fatty acid spectrum in the storage fats of oil plants. In the context of the present invention, preferred fatty acids have a melting point which allows these fats to be processed as a material or as a component of a casting. Fatty acids which have a melting point above 25 ° C. have proven particularly advantageous. Preferred matrix materials and / or constituents are therefore capric acid and / or undecanoic acid and / or lauric acid and / or tridecanoic acid and / or myristic acid and / or pentadecanoic acid and / or palmitic acid and / or margaric acid and / or stearic acid and / or nonadecanoic acid and / or arachic acid and / or erucic acid and / or eiaeosteraric acid. But also fatty acids with a melting point below 25 ° C can be used as a component of the matrix for castings or other solids mentioned above.

Fatty alcohol is a collective name for the linear, saturated or unsaturated primary alcohols with 6 to 22 carbon atoms that can be obtained by reducing the triglycerides, fatty acids or fatty acid esters. The fatty alcohols can be saturated or unsaturated depending on the manufacturing process. Myristyl alcohol and / or 1-pentadecanol and / or cetyl alcohol and / or 1-heptadecanl and / or stearyl alcohol and / or erucyl alcohol and / or 1-nonadecanol and / or arachidyl alcohol and / or 1-heneicosanol and / or behenyl alcohol and / or Erucyl alcohol and / or brassidyl alcohol are preferred components of the matrix of castings or other solids enclosed by the containers produced according to the invention.

It has also proven to be advantageous if the solids enclosed in the containers produced according to the invention, in particular the preferably enclosed casting bodies, contain waxes as matrix material. Preferred waxes have a melting range that is between about 4 δ ° C and about 7 δ ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Waxes with such a melting range are on the one hand dimensionally stable at room temperature, but melt at temperatures of 30 ° C. to 90 ° C. which are typical for machine dishwashing and are therefore more readily water-dispersible at these temperatures.

"Waxing" is understood to mean a number of natural or artificially obtained substances which, as a rule, melt above 40 ° C. without decomposition and are relatively low-viscosity and not stringy just above the melting point. They have a strongly temperature-dependent consistency and solubility.

The waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax,

Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, Ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, mineral waxes such as ceresin or ozokerite (earth wax), or petroleum chemicals , Paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Are reversed synthetic or semi-synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as a matrix material in solids, preferably in castings.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co).

In a further preferred embodiment, one or more of the solids enclosed in the containers produced according to the invention, but preferably a casting made by solidification, predominantly contains paraffin wax (parrafins) as the matrix material. This means that at least 50% by weight of the total meltable or softenable substances contained, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total weight of the matrix materials) of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred , In a particular embodiment of the invention, the entire material of one or more of the solids filled into the containers produced according to the invention consists of paraffin wax.

Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that when the containers produced according to the invention are used as dosing units for detergents and cleaning agents in an alkaline cleaning agent environment, there is no hydrolysis of the waxes (as is the case, for example, with the wax esters is to be expected) since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Preferred solids, in particular castings, contain at least one paraffin wax with a melting range of 40 ° C. to 60 ° C. as matrix material and / or matrix constituent.

Preferably, the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally about 10 to about 30 ° C.) is as high as possible. The more solid wax components present in a wax at room temperature, the more useful it is within the scope of the present invention.

Further advantageous constituents of the matrix of solids, in particular castings, are wax alcohols, i.e. fatty alcohols with approx. 24-36 carbon atoms, which are the main constituent of many natural waxes in the form of wax esters of higher molecular weight fatty acids (wax acids). Examples of preferred wax alcohols are lignoceryl alcohol, ceryl alcohol, myricyl alcohol or melissyl alcohol.

Dispersions are particularly suitable for processing as castings, dispersions with washing or cleaning-active substances or mixtures of active substances being used with particular preference. In a particularly preferred embodiment of the present application, the washing- or cleaning-active preparation used to produce the casting is a dispersion of solid particles in a dispersing agent, dispersions which, based on their total weight i), 10 to 85% by weight of dispersing agent and ii) contain 15 to 90% by weight of dispersed substances, are particularly preferred.

In this application, dispersion is a system consisting of several phases, one of which is continuous (dispersant) and at least one other is finely divided (dispersed substances).

Particularly preferred dispersions are characterized in that they contain the dispersant in amounts above 11% by weight, preferably above 13% by weight, particularly preferably above 1δ% by weight, very particularly preferably above 17% by weight and in particular above 19% by weight, based in each case on the total weight of the dispersion. Dispersions which have a dispersion with a proportion by weight of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, in each case based on the total weight of the dispersion, can furthermore preferably be used. The maximum content of dispersions in preferred dispersions, based on the total weight of the dispersion, is preferably less than 63% by weight, preferably less than 67% by weight, particularly preferably less than 62% by weight, very particularly preferably less than 47% by weight .-% and in particular less than 37 wt .-%. Within the scope of the present invention Especially those active washing or cleaning preparations which, based on their total weight, contain dispersing agents in amounts of 12 to 62% by weight, preferably 14 to 49% by weight and in particular 16 to 38% by weight. Dispersions with a dispersant content of between 16 and 30% by weight, preferably between 16 and 26% by weight and in particular between 16 and 22% by weight, in each case based on the total weight of the dispersion, are particularly preferred.

The dispersants used are preferably water-soluble or water-dispersible. The solubility of these dispersants at 25 ° C. is preferably more than 200 g / l, preferably more than 300 g / l, particularly preferably more than 400 g / l, very particularly preferably between 430 and 620 g / l and in particular between 470 and 580 g / l.

Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers. The dispersant can be either a single polymer or a mixture of different water-soluble or water-dispersible polymers. In a further preferred embodiment of the present invention, the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, vinylpyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula III

H- (0-CH ₂ -CH ₂ ) _n -OH (III)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols which can lead to confusion. The specification of the average relative molecular weight after the specification "PEG" is so common in technical terms, so that "PEG 200" is a polyethylene glycol with a relative molecular weight of approx. 190 to approx. 210 characterized. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula VII mentioned above. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG-9 , PEG-10, PEG-12, PEG- 14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), üpoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone - Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers. The average relative molecular weight of at least one of the dispersants used in the washing or cleaning agents according to the invention, in particular at least one of the poly (alkylene) glycols used, is preferably between 200 and 36,000, preferably between 200 and 6000 and particularly preferably between 300 and δOOO.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula IV

H- (0-CH-CH ₂ ) _n -OH (IV)

CH ₃

are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Technically important here are in particular di-, tri- and tetrapropylene glycol, i.e. the representatives with n = 2, 3 and 4 in formula IV.

Dispersions are particularly preferably used which contain a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the proportion by weight of the poly (ethylene) glycol in the total weight of all dispersion media is preferably between 10 and 90% by weight, particularly preferably between 30 and 80% by weight and in particular between δO and 70% by weight. Dispersions in which the dispersant is more than 92% by weight, preferably more than 94% by weight, particularly preferably more than 96% by weight, very particularly preferably more than 98% by weight are particularly preferred. and in particular 100% by weight of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular poly (ethylene) glycol. Dispersing agents which, in addition to poly (ethylene) glycol, also contain poly (propylene) glycol, preferably have a ratio by weight of poly (ethylene) glycol to poly (propylene) glycol of between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, particularly preferably between 10: 1 and 1, 6: 1 and in particular between 7: 1 and 2: 1.

Further preferred dispersants are the nonionic surfactants, which are used both alone, but particularly preferably in combination with a nonionic polymer become. Detailed information on the nonionic surfactants that can be used can be found below in the description of detergent or cleaning substances.

Dispersions which are preferably used are characterized in that at least one dispersant has a melting point above 2δ ° C, preferably above 3δ ° C and in particular above 40 ° C. Particularly preferred is the use of dispersants with a melting point or melting range between 30 and 80 ° C, preferably between 35 and 75 ° C, particularly preferably between 40 and 70 ° C and in particular between 4δ and 6δ ° C, these dispersants based on the total weight of the dispersants used, a weight fraction above 10% by weight, preferably above 40% by weight, particularly preferably above 70% by weight and in particular between 60 and 100% by weight.

Suitable dispersed substances in the context of the present application are all substances which are active in washing or cleaning at room temperature, but in particular substances which are active in washing or cleaning from the group of builders (builders and cobuilders), active polymers for washing or cleaning, bleaching agents and bleach activators , the glass corrosion protection agent, the silver protection agent and / or the enzymes. A more detailed description of these ingredients can be found below in the text.

The water content of the dispersions preferably used in the process according to the invention is, based on their total weight, preferably less than 30% by weight, preferably less than 23% by weight, preferably less than 19% by weight, particularly preferably less than 1δ % By weight and in particular less than 12% by weight. Dispersions preferably used according to the invention are low in water or anhydrous. Dispersions used with particular preference are characterized in that, based on their total weight, their free water content is below 10% by weight, preferably below 7% by weight, particularly preferably below 3% by weight and in particular below 1% by weight. -% exhibit.

The dispersions, which are preferably used as washing or cleaning active preparations, are distinguished by a high density. Dispersions with a density above 1.040 g / cm ³ are particularly preferably used. Preferred methods according to the invention are characterized in that the washing and cleaning active preparation has a density above 1.040 g / cm ³ , preferably above 1.1 δ g / cm ³ , particularly preferably above 1.30 g / cm ³ and in particular above 1 , 40 g / cm ³ . This high density not only reduces the total volume of a dosing unit cast body but also improves its mechanical stability. Particularly preferred methods according to the invention are therefore characterized in that the dispersion preferably has a density between 1.0δ0 and 1.670 g / cm ³ between 1, 120 and 1, 610 g / cm ³ , particularly preferably between 1, 210 and 1, 670 g / cm ³ , very particularly preferably between 1, 290 and 1, 610 g / cm ³ , and in particular between 1, 340 and 1. 480 g / cm ^3. The information on the density relates in each case to the densities of the compositions at 20 ° C. In order to avoid segregation processes during the processing of these dispersions, in particular in the course of the vibration of the molds, dispersing agents and dispersed substances preferably have densities which are less than 0.6 g / cm ³ , preferably less than 0.4 g / cm ³ and differ in particular by less than 0.3 g / cm ³ .

Dispersions preferably used according to the invention as a detergent or cleaning preparation are distinguished in that they disperse in water (40 ° C.) in less than 9 minutes, preferably less than 7 minutes, preferably in less than 6 minutes, particularly preferably in less than δ Minutes, especially in less than 4 minutes. To determine the solubility, 20 g of the dispersion are introduced into the interior of a dishwasher (Miele G 646 PLUS). The main wash cycle of a standard wash program (45 ° C) is started. The solubility is determined by measuring the conductivity, which is recorded by a conductivity sensor. The dissolving process ends when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau. The conductivity measurement begins with the insertion of the circulation pump in the main wash cycle. The amount of water used is 5 liters.

Dimensionally stable gels are another solid which is particularly preferred in the context of the present invention. The term “dimensionally stable” here means gels which have an inherent shape stability which enables them to assume a non-disintegrating spatial form which is stable against breakage and which under normal conditions of manufacture, storage, transport and handling by the consumer, whereby these form Spatial shape under the conditions mentioned, even over a longer period of time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, has not changed, that is to say under the usual conditions of manufacture, storage, transport and handling by the consumer in the the production-related spatial-geometric form persists, that is, does not flow, for example, or returns to this spatial-geometric form under the influence of an external force customary under the conditions of production, storage, transport and handling.

In order to achieve the desired dimensional stability, the gels with good product properties (solubility, washing and cleaning performance, stability of the gel), it is preferred in the context of the present invention to use one or more substances from the group agar-agar, carrageenan, Tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose, Kemmehlether, Polyacryl- u. Contain polymethacrylic, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas, it having proven to be particularly advantageous if the gels contain these or one of the following thickeners in amounts between 0.2 and 10 % By weight, preferably between 0.3 and 7% by weight and particularly preferably between 0.4 and 4% by weight, based on the total weight of the shaped body.

Polymers derived from nature, which are used as thickeners in the context of the present invention, are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, as described above and casein.

Modified natural products come primarily from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.

A large group of thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Thickeners from these substance classes are widely available commercially and are sold, for example, under the trade names Acusol ^® -820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^® -GT-232 -S (alkyl polyglycol ether, Akzo), Deuterol ^® polymer 11

(Dicarboxylic acid copolymer, Schönes GmbH), Deuteron ^® -XG (anionic heteropolysaccharide based on β-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron ^® -XN (non-ionic polysaccharide, Schönes GmbH), dicrylan ^® thickener-0 (ethylene oxide adduct, 60% in water / isopropanol, Pfersse Chemie), EMA ^® -δ1 and EMA ^® -91

(Ethylene-maleic anhydride copolymer, Monsanto), thickener-QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylic ester copolymer dispersion, 26% ig in Wasser, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^® -S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo ^® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell) offered.

Due to their manufacturing process and to optimize their dissolving behavior, preferred gels contain various solvents, gels having proven particularly advantageous in terms of their product properties, the water and / or one or more water-miscible solvents in amounts of 5 to 70% by weight, preferably of Contain 10 to 6δ wt .-% and particularly preferably from 15 to 60 wt .-%. It has also proven to be particularly advantageous if the water-miscible solvents contain one or more substances from the group consisting of ethanol, n- or i-propanol, n- or sec- or tert-butanol, glycol, propane or butanediol, glycerol, Diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether,

Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3- contain methoxybutanol, propylene glycol t-butyl ether.

The capsules are further preferred solids enclosed in containers produced according to the invention. "Capsule" is a term for a frequently used form of packaging that contains solid, semi-solid or liquid substances in differently sized, possibly colored, layers of gelatin, wax or wafer material. The most common are the gelatin capsules (made of hard or soft Gelatin).

In a special embodiment of the present invention, one or more or all of the solids filled into the containers produced according to the invention, ie for example one, several or all of the powders and / or granules and / or extrudate (s) filled into these containers. and / or compact (s) and / or cast body and / or dimensionally stable gel (s) and / or capsule (s), a coating (coating). Such a coating can serve different purposes. On the one hand, coating can, for example, prevent undesired contact of active substances which are sensitive to hydrolysis or oxidation in the solids, with the outside air or other solids enclosed in the water-soluble container according to the invention. On the other hand, an advantageous visual effect can also be achieved by a coating.

Liquids and solids are suitable as ingredients for the receiving chambers or spaces. In the case of solids, a distinction is made between powders, granules, extrudates, compactates, castings and dimensionally stable gels. In the context of this application, liquids are not only low-viscosity, flowable liquids or flowable gels, but also flowable dispersions, for example emulsions or suspensions. Active substances or combinations of active substances are considered to be flowable if they have no inherent dimensional stability which enables them to assume a non-disintegrating spatial form under the usual conditions of manufacture, storage, transport and handling by the consumer, this spatial form under the conditions mentioned not changed over a longer period of time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, that is under the usual conditions of Production, storage, transport and handling by the consumer remains in the spatial-geometric shape resulting from the production, that is, does not melt. The determination of the flowability relates in particular to the conditions customary for storage and transport, that is to say in particular to temperatures below 50 ° C., preferably below 40 ° C. Liquids are therefore in particular active substances or combinations of active substances with a melting point below 25 ° C., preferably below 20 ° C., particularly preferably below 1 δ ° C.

The following tables list the containers that can be produced using two or three filled receptacles according to the preferred methods of the invention. The receiving troughs filled with liquid, powder or granules preferably have a seal. In the case of the receiving troughs filled with compactates, extrudates, castings or dimensionally stable gels, the sealing is optional, but is preferred.

Container with two receiving chambers

Container with three receiving chambers

Processes according to the invention which are particularly preferred in the context of the present application are characterized in that at least one receiving chamber is filled with a liquid, at least one further receiving chamber is filled with a solid. Methods according to the invention are particularly preferably at least one receiving chamber with a casting body (melt), at least one further receiving chamber is filled with a solid.

As mentioned at the beginning, the method according to the invention is suitable for portioning, packaging and metering active substances or active substance mixtures. In preferred embodiments of the method according to the invention, the substances or mixtures of active substances contained in the substances in the fields of pharmaceuticals, cosmetics, feed, crop protection agents or fertilizers, adhesives, foods and / or personal care agents, but preferably in the area of washing and cleaning-active substances.

Preferred active substances or mixtures of active substances from the field of cosmetics are, in particular, hair setting agents, hair shaping agents and hair coloring agents. In addition to hair washing and hair care products, the preferred personal care products also include pre-treatment agents, hairdressing aids and course rinses. Active substances from the area of bath additives, such as bath salts or bath tablets, but also shower, foam or cream baths, are also preferred.

A particularly preferred method according to the invention is characterized in that the agent (s) filled in are detergents or cleaning agents. Washing and cleaning-active substances from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes,

Disintegration aids, electrolytes, pH regulators, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, anti-redeposition agents, optical brighteners,

Graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, phobicants and impregnants, swelling and anti-slip agents, non-aqueous solvents, fabric softeners, UV absorbers and protein hydrolyzers. Bleaching agents and bleach activators can be included in the agents produced according to the invention as important components of detergents and cleaning agents. Among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or

Diperdodecanedioic. Detergent tablets for automatic dishwashing can also contain bleaches from the group of organic bleaches. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidonic acid hydroxyproxy

[Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyacidacidacidacidacidacid Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

If the agents produced according to the invention are used as automatic dishwashing agents, they can contain bleach activators in order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1, δ-diacetyl-2,4-dioxohexahydro-1, 3, δ-triazine (DADHT), acylated glycolurils, in particular tetraacetyiglycolouril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate diacetate and ethylene glycol 2 2,5-dihydrofuran. Further bleach activators which are preferably used in the context of the present application are compounds from the group of the cationic nitriles, in particular cationic nitrile of the formula

R ¹

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ^H ,

R ³

in R ¹ for -H, -CH ₃ , a C ₂ . ₂₄ alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι. ₂₄ alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ³ are selected independently of one another from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ - CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -0) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

A particularly preferred agent according to the invention is a cationic nitrile of the formula

R ⁴

R ⁵ -N oυ (CH ₂ ) -CN X »,

R ⁶

contain, in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ^{4 can} additionally be -H and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ^{( +)} CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{" are} particularly preferred, again from the group of these substances the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , in which X ^{" represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is selected, is particularly preferred.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the agents. These substances are are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

The surfactants include in particular the anionic surfactants in acid form, aqueous solutions or pastes of the neutralized anionic surfactant acids, nonionic surfactants and / or cationic surfactants or amphoteric surfactants. Depending on the choice of the surfactant (s) used, surfactant-containing agents produced according to the invention can be used, for example, in the removal of grease or oil soiling, their field of use extending from textile cleaning to the removal of oil soiling in nature. In the context of the present application, granules are preferred which have a surfactant content of 1 to 70% by weight, particularly preferably 2 to 60% by weight, particularly preferably 4 to 50% by weight, in each case based on the total weight of the compositions , exhibit.

In addition to the bleaching agents and bleaching agent mentioned, builders are other important ingredients of detergents. Preferred agents produced according to the invention can contain all builders usually used in cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates. The builders mentioned can of course also be used in surfactant-free compressed products.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 ₂ χ ₊ ι 'H ₂ 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x is 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ 0 ₅ ^" yH ₂ 0 are preferred.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered ones X-rays having a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite that can be used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ 0 '(1-n) K ₂ 0 ^• Al ₂ 0 ₃ ^' (2 - 2.5) Si0 ₂ ^' (3.5 - 5, δ) H ₂ 0

can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 in addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.

Nat umdihydrogenphosphat, NaH ₂ P0, disodium hydrogenphosphate (secondary

Sodium phosphate), Na ₂ HP0 ₄ , trisodium phosphate, tertiary sodium phosphate, Na ₃ P0 ₄ , Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ 0 ₇ and condensation of the NaH ₂ P0 ₄ or the KH ₂ P0 ₄ result in higher mol. Sodium and potassium phosphates, in which one can differentiate between cyclic representatives, the sodium and potassium metaphosphates and chain-like types, the sodium and potassium polyphosphates, as well as the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) are further within the scope of the present Registration with advantage used builders.

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their alkali and in particular sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons and mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances are considered to be alkali carriers, alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium bicarbonate being used for the purposes of this invention.

If the agents produced according to the invention are used in automatic dishwashing, water-soluble builders are preferred, since they generally have less tendency to form insoluble residues on dishes and hard surfaces. Common builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicate and / or metasilicate are preferably used for the production of tablets for machine dishwashing. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system which contains a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.

Organic cobuilders which can be used in the cleaning agents in the context of the present invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below. Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of δOO to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permealion chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, can in turn be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below. However, it is also possible to provide agents produced according to the invention, which combine the conventional cleaners, rinse aids and a salt replacement function as so-called “3in1” products. For this purpose, machine dishwashing agents manufactured according to the invention are preferred, which additionally contain 0.1 to 70% by weight of copolymers

i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionic monomers

contain.

These copolymers have the effect that the items of tableware treated with such agents become significantly cleaner in subsequent cleaning operations than items of tableware that have been washed with conventional agents.

In the context of the present invention, unsaturated carboxylic acids of the formula I are preferred as the monomer

R ¹ (R ² ) C = C (R ³ ) COOH (I),

in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by formula I are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H; R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) preferred.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula II

R ⁵ (R ⁶ ) C = C (R ^r ) -X-S0 ₃ H (II),

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, single or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or - COOH as defined above or represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms, and X represents an optionally available spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas IIa, IIb and / or IIc,

H ₂ C = CH-X-S0 ₃ H (Ila),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (llb),

H0 ₃ SX- (R ⁶ ) C = C (R ^r ) -X-S0 ₃ H (llc),

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH- CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₂ CH ₃ ) in formula IIIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( 0) NH-C (CH ₃ ) ₂ in formula Ila), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH-C (CH ₃ ) ₂ CH ₂ - in formula Ila), 2-Melhacrylamido-2-melhyl-1-propanesulfonic acid (X = -C (0) NH- C (CH ₃ ) ₂ CH ₂ - in formula IIb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C ( 0) NH- CH ₂ CH (OH) CH ₂ - in formula IIb) allyl sulfonic acid (X = CH ₂ in formula IIa), methallyl sulfonic acid (X = CH ₂ in formula IIb), allyloxybenzenesulfonic acid (X = -CH ₂ -0- C ₆ H ₄ - in formula IIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H ₄ - in formula Xlb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene1 -sulfonic acid (X = CH ₂ in formula IIb), styrene sulfonic acid (X = C ₆ H ₄ in formula IIa), vinylsulfonic acid (X not present in formula IIa), 3- acrylamido-propanesulfonic acid (X = -C (0) NH- CH ₂ CH ₂ CH ₂ - In formula Ila), 3-methacrylic amido-propanesulfonic acid (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in formula IIb), sulfomethacrylamide (X = -C (0) NH- in formula IIb), sulfomethyl methacrylamide (X = -C (0) NH-CH ₂ - in formula IIb) and water-soluble salts of the acids mentioned.

Other suitable ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of monomers of group iii) in the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii). In summary, copolymers are made of

i) unsaturated carboxylic acids of formula I.

R ¹ (R ² ) C = C (R ³ ) COOH (I),

in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,

ii) Monomers of the formula il containing sulfonic acid groups

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (II),

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH- CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

Particularly preferred copolymers consist of

i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid ii) one or more monomers of the formulas IIa, IIb and / or IIc containing sulfonic acid groups:

H ₂ C = CH-X-S0 ₃ H (Ila),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (llb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (llc),

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _π - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH- C (CH ₃ ) ₂ - and - C (0) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers.

The copolymers contained in the compositions can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined. Particularly preferred polymers have certain structural units, which are described below.

For example, agents produced according to the invention are preferred which are characterized in that they contain one or more copolymers which contain structural units of the formula III

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (III),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IV - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (IV),

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Agents according to the invention which contain one or more copolymers which contain structural units of the formula V

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (V),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are also preferred, a preferred embodiment of the present invention, just as preferred are agents which are characterized in that they contain one or more copolymers which have structural units of the formula VI

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (VI),

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula VII

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VII), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred, and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula VIII

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (VIII),

In summary, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (III),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (IV),

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (V),

- [CH ₂ -C (CH ₃ ) C00H] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (VI),

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VII),

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (VIII),

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

All or part of the sulfonic acid groups in the polymers can be present in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. Corresponding means, which are characterized by that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.

The monomer distribution of the copolymers used in the agents according to the invention is preferably δ to 95% by weight i) or ii), particularly preferably 50 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii). % Monomer from group i) and 10 to δO% by weight monomer from group ii), in each case based on the polymer.

In the case of terpolymers, those which contain 20 to δδ% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and δ to 30% by weight of monomer from group iii) are particularly preferred ,

The molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^"1 , preferably from 4000 to 2δ,000 gmol ^{" 1} and in particular from δOOO to 16,000 gmol ^"1 .

The content of one or more copolymers in the agents according to the invention can vary depending on the intended use and the desired product performance, preferred dishwasher detergents according to the invention being characterized in that they contain the copolymer (s) in amounts of 0.25 to 50% by weight. %, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight.

As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention. The polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred. Such polyacrylates are commercially available under the trade names Sokalan ^® PA15 or Sokalan ^® PA26 (BASF).

Preferred agents produced according to the invention, which are used as automatic dishwashing agents, can furthermore contain amphoteric or cationic polymers to improve the rinse aid result as dispersed substances. These particularly preferred polymers are characterized in that they have at least one positive charge. Such polymers are preferably water-soluble or water-dispersible, that is to say they have a solubility in water at 2 ° C. above 10 mg / ml.

Cationic or amphoteric polymers particularly preferably contain at least one ethylenically unsaturated monomer unit of the general formula

R ¹ (R ² ) C = C (R ³ ) R ⁴

in which R to R ⁴ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , - OH or --COOH substituted alkyl or alkenyl radicals as defined above, a heteroatomic group with at least one positively ended group, a quaternized nitrogen atom or at least one amine group with a positive charge in the pH range between 2 and 11 or for -COOH or -COOR ⁵ stands, wherein R ^{5 is} a saturated or unsaturated, straight-chain or branched hydrocarbon residue with 1 to 12 carbon atoms.

Examples of the aforementioned (non-polymerized) monomer units are diallylamine, methyldiallylamine, dimethyldimethylammonium salts, acrylamidopropyl (trimethyl) ammonium salts (R ¹ , R ² , and R ³ , H, R ⁴ = C (0) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X ^D ),

Methacrylic amidopropyl (trimethyl) ammonium salts (R ¹ and R ² = H, R ³ = CH ₃ H, R ⁴ = C (0) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X ^u ).

Unsaturated carboxylic acids of the general formula are particularly preferred as a constituent of the amphoteric polymers

R ¹ (R ² ) C = C (R ³ ) COOH

used, in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents - COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred amphoteric polymers contain derivatives of diallylamine, especially dimethyldiallylammonium salt and / or as monomer units

Methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of the chloride, bromide, iodides, hydroxides, phosphates, sulfates, hydrosulfates, ethyl sulffasts, methyl sulfates, mesylates, tosylates, formates or acetates in combination with monomer units from the group of the ethylenically unsaturated carboxylic acids.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 60,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the agents is preferably from 0.1 to 20% by weight, in particular from 3 to 10% by weight.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,

Anionic surfactants in acid form are preferably one or more substances from the group of carboxylic acids, sulfuric acid half-esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylarylsulfonic acids. In order to have sufficient surface-active properties, the compounds mentioned should have longer-chain hydrocarbon radicals, that is to say they should have at least 6 carbon atoms in the alkyl or alkenyl radical. The C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably δ to 30 and in particular 12 to 22 carbon atoms.

Carboxylic acids, which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous High pressure hydrolysis. Carboxylic acids which can be used as an anionic surfactant in acid form in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. In the context of the present compound, preference is given to Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacidic acid (melotinic acid), triacidic acid (melotonic acid), and melonic acid unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidinic acid), 9c, 12c-octadecenoic acid) (9c -Octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c- Octadecatreinsäu re (linolenic acid) For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids that are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% C ₁₈ , 8 wt .-% C ₁₈ -, 1 wt .-% Ciβ "). Palm kernel oil fatty acid (approx. 4 wt .-% C ₈ , 5 wt .-% C ₁₀ , δO wt .-% Cι _2, 16 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 16 wt .-% _w C, 1 wt .-% C ₁₈ -), tallow fatty acid (about 3 wt .-% C ₁₄ , 26 wt .-% C ₁₆ , 2 wt .-% C ₁₆ -, 2 wt .-% C ₁₇ , 17 wt .-% C ₁₈ , 44 wt .-% C ₁₈ -, 3 wt .-% C ₁₈ -, 1 wt.% C ₁₈ "-) _> hardened tallow fatty acid (approx. 2 wt.% C ₁₄ , 28 wt.% C ₁₆ , 2 wt.% C ₁₇ , 63 wt. -% C ₁₈ , 1% by weight C ₁₈ -), technical oleic acid (approx. 1% by weight C ₁₂ , 3% by weight C ₁₄ , 5% by weight C ₁₆ , 6% by weight C) ₁₆ -, 1 wt.% C ₁₇ , 2 wt.% C ₁₈ , 70 wt.% C ₁₈ -, 10 wt.% C ₁₈ -, 0.5 wt.% C ₁₈ -) _> technical palmitic / Slearinsäure (about 1 wt .-% C _12, 2 wt .-% C ₁₄ 45 wt .-% C _16, 2 wt .-% C _1, 47 wt .-% Cι _8, 1 wt % C-ι ₈ -) and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15 % By weight C ₁₆ , 5% by weight C ₁₈ , 2δ% by weight C ₁₈ -, 4δ% by weight C ₁₈ ^» , 7% by weight C ₁₈ -).

Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the context of the present invention. Their alkali metal, in particular sodium salts, the fatty alcohol sulfates, are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized. The fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters. The most important industrial process in terms of quantity for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

Another class of anionic surfactant acids which can be used according to the invention are the alkyl ether sulfuric acids, their salts, the alkyl ether sulfates, which are more soluble in water and less sensitive to the alkyl sulfates Characterize water hardness (solubility of Ca salts). Like the alkyl sulfuric acids, alkyl ether sulfuric acids are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the alkyl ether sulfuric acids concerned.

Alkanesulfonic acids and olefin sulfonic acids can also be used as anionic surfactants in acid form in the context of the present invention. Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the carbon chain (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons. In Reed sulfochlorination, n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to give the corresponding sulfochlorides, which, when hydrolysed with alkalis, provide the alkanesulfonates directly, and when reacted with water, the alkanesulfonic acids. Since di- and polysulfochlorides and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually carried out only up to degrees of conversion of 30% and then terminated.

Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins are reacted with sulfur dioxide and oxygen under irradiation with UV light. This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylpersulfonyl radicals. The reaction with unreacted paraffin gives an alkyl radical and the alkyl persulfonic acid, which breaks down into an alkyl peroxysulfonyl radical and a hydroxyl radical. The reaction of the two radicals with unreacted paraffin gives the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to give sulfuric acid. In order to keep the yield of the two end products alkylsulfonic acid and sulfuric acid as high as possible and to suppress side reactions, this reaction is usually carried out only up to degrees of conversion of 1% and then stopped.

Olefin sulfonates are produced industrially by the reaction of α-olefins with sulfur trioxide. Intermediate hermaphrodite ions are formed, which cyclize into so-called suitons. Under suitable conditions (alkaline or acidic hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which can also be used as anionic surfactant acids. Alkylbenzenesulfonates as powerful anionic surfactants have been known since the 1930s. At that time, alkylbenzenes were produced by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution. In the early 1950s, to produce alkylbenzenesulfonates, propylene was tetramerized to give branched α-dodecylene and the product was converted to tetrapropylene benzene via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride, which was subsequently sulfonated and neutralized. This economical possibility of producing tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, which subsequently displaced the soaps as the main surfactant in washing and cleaning agents.

Due to the lack of biodegradability of TPS, there was a need to prepare new alkylbenzenesulfonates that are characterized by improved ecological behavior. These requirements are met by linear alkyl benzene sulfonates, which today are almost exclusively alkyl benzene sulfonates and are given the abbreviation ABS or LAS.

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins. For this purpose, petroleum fractions with molecular sieves are separated on an industrial scale into the n-paraffins of the desired purity and dehydrated to the n-olefins, resulting in both - and i-olefins. The resulting olefins are then reacted with benzene in the presence of acidic catalysts to give the alkylbenzenes, the choice of Friedel-Crafts catalyst having an influence on the isomer distribution of the linear alkylbenzenes formed: when using aluminum trichloride, the content of the 2-phenyl isomers is in the mixture with the 3, 4, 5 and other isomers at approx. 30% by weight, on the other hand, if hydrogen fluoride is used as a catalyst, the content of 2-phenyl isomer can be reduced to approx. 20% by weight , Finally, the sulfonation of linear alkylbenzenes is now possible on a large industrial scale with oleum, sulfuric acid or gaseous sulfur trioxide, the latter being by far the most important. For the sulfonation, special film or tube bundle reactors are used which deliver a 97% by weight alkylbenzenesulfonic acid (ABSS) as product, which can be used as anionic surfactant acid in the context of the present invention.

By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred to prepare and use the alkali metal salts and, among them, the sodium salts of the ABSS. These can be described by the general formula IX:

in which the sum of x and y is usually between 5 and 13. According to the invention, the preferred anionic surfactant in acid form is C _8-16 -, preferably C _9-13 -alkylbenzenesulfonic acids. It is further preferred in the context of the present invention to use C _8-16 -, preferably C _9-13 - alkylbenzenesulfonic acids which are derived from alkylbenzenes which have a tetralin content below δ% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes were produced by the HF process, so that the C _8-16 -, preferably C ₉ - used. _13- Alkylbenzenesulfonic acids have a 2-phenyl isomer content below 22% by weight, based on the alkylbenzenesulfonic acid.

The above-mentioned anionic surfactants in their acid form can be used alone or in a mixture with one another. However, it is also possible and preferred that the anionic surfactant in

Acid form before addition to the carrier material (s) further, preferably acidic, ingredients of detergents and cleaning agents in amounts of 0.1 to 40% by weight, preferably 1 to 15% by weight and in particular 2 to 10% by weight, based in each case on the weight of the mixture to be reacted, are admixed.

Suitable acidic reactants in the context of the present invention are, in addition to the “surfactant acids”, also the fatty acids, phosphonic acids, polymer acids or partially neutralized polymer acids as well as “builder acids” and “complex builder acids” (details later in the text) alone and in any mixtures. As ingredients of washing Acid detergents and cleaning agents are particularly suitable, for example phosphonic acids, which in neutralized form (phosphonates) are components of many detergents and cleaning agents as incrustation inhibitors. The use of (partially neutralized) polymer acids such as polyacrylic acids is also an option According to the invention, it is also possible to mix acid-stable ingredients with the anionic surfactant acid, for example so-called small components, which would otherwise have to be added in complex further steps, for example se optical brighteners, dyes etc., whereby the acid stability must be checked in individual cases. Of course, it is also possible to use the anionic surfactants partially or fully neutralized. These salts can then be present as a solution, suspension or emulsion in the granulating liquid, but can also be part of the solid bed as a solid. In addition to the alkali metals (here in particular according to claim and K salts), ammonium and mono-, di- or triethanolalkonium ions are suitable cations for such anionic surfactants. Instead of mono-, di- or triethanolamine, the analog representatives of mono-, di- or trimethanolamine or those of the alkanolamines of higher alcohols can also be quaternized and present as a cation.

Cationic surfactants can also be used with advantage as active substances. The delivery form of the cationic surfactant can be added directly to the mixer, or it can be sprayed onto the solid carrier in the form of a liquid to pasty form of cationic surfactant. Such cationic surfactant preparation forms can be prepared, for example, by mixing commercially available cationic surfactants with auxiliaries such as nonionic surfactants, polyethylene glycols or polyols. Lower alcohols such as ethanol and isopropanol can also be used, the amount of such lower alcohols in the liquid cationic surfactant preparation form being below 10% by weight for the reasons mentioned above.

All customary substances are suitable as cationic surfactants for the agents according to the invention, cationic surfactants having a fabric softening effect being clearly preferred.

The agents according to the invention can contain, as cationic active substances with a fabric softening effect, one or more cationic, fabric softening agents of the formulas X, XI or XII:

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (X)

(CH ₂ ) _n -TR ²

R ¹

R -N ⁽⁺ '- (CH ₂ ) _n -CH-CH ₂ (XI)

R ¹ TT

R ² R ²

R ¹

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (XII)

R

wherein each group R ^{1 is} independently selected from Cι. ₆ alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O- CO- or -CO-O- and n is an integer from 0 to 5.

In preferred embodiments of the present invention, the solid (s) additionally contain nonionic surfactant (s) as active substance.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-1 - Alcohols with 3 EO or 4 EO, Cg.n alcohol with 7 EO, C ₁₃ . ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ . ₁ alcohol with 3 EO and C ₁₂ . ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 26 EO, 30 EO or 40 EO.

In the context of the present invention, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. Among these, surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Agents according to the invention which contain surfactants of the general formula XIII as nonionic surfactant (s) are preferred here

R ¹ -0- (CH ₂ -CH ₂ -0) _w - (CH ₂ -CH-0) _x - (CH ₂ -CH ₂ -0) _y - (CH ₂ -CH-0) _z -H (XIII )

I I

R ² R ³

in which R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently represent integers from 1 to 6.

The preferred nonionic surfactants of the formula XIII can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethyl or alkylene oxide. The radical R ¹ in the above formula XIV can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally not shown, the linear radicals being of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. Regardless of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, compositions prepared according to the invention are preferred in which R ¹ in formula XIV for an alkyl radical having 6 to 24, preferably δ to 20, particularly preferably 9 to 15 and in particular 9 is up to 11 carbon atoms. In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from - CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are also suitable. Preferred agents are characterized in that R ² or R ³ for a radical -CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants which have a C ₉ . ₁₅ - alkyl having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula (XIV)

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x R ² (XIV)

in which R ^{1 stands} for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R ² for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon monomers, which preferably is between 1 and δ have hydroxyl groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n-propyl, isopropyl, n-bulyl, 2-butyl or 2-methyl-2- Butylresl stands for x between 1 and 40.

In the case of particularly preferred nonionic surfactants of the above formula (XIV), R ^{3 is} H. In the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula (XV)

R ¹ 0 [CH ₂ CH ₂ 0] _x R ² (XV)

those nonionic surfactants are particularly preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and δ hydroxyl groups and x stands for values between 1 and 40. In particular, those end group-capped poly (oxyalkylated) nonionic surfactants which are of the formula (XVI)

R ¹ 0 [CH ₂ CH ₂ 0] _x CH ₂ CH (OH) R ² (XVI)

in addition to a radical R ¹ , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 have up to 30 carbon atoms R ² , which is adjacent to a monohydroxylated intermediate group - CH ₂ CH (OH). x in this formula stands for values between 1 and 40. Such end-capped poly (oxyalkylated) nonionic surfactants can be obtained, for example, by reacting a terminal epoxide of the formula R ² CH (0) CH ₂ with an ethoxylated alcohol of the formula R ^ CHzCHzOj ^ CHzCHzOH.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation represent statistical mean values which can be an integer or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers both for the C chain lengths and for the degrees of ethoxylation or alkoxylation.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R a primary straight-chain or methyl branching, in particular in the 2-position methyl branched aliphatic radical with δ to 22, preferably 12 to 1δ C atoms and G is the symbol which stands for a glycose unit with δ or 6 C atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.

Also nonionic surfactants of the amine oxide type, for example N-coconut alky-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula XVII,

R ¹

R-CO-N- [Z] (XVII)

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula XVIII,

R ¹ -0-R ²

R-CO-N- [Z] (XVIII)

in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical is 2 to δ carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to δ carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this remainder.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. For many applications it is particularly preferred if the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2 is. Preferred are containers according to the invention which contain surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to δO% by weight, preferably from 7, δ to 70% by weight. %, particularly preferably from 10 to 60% by weight and in particular from 12.5 to 50% by weight, in each case based on the weight of the enclosed solids.

As already mentioned, the use of surfactants in cleaning agents for automatic dishwashing is preferably limited to the use of nonionic surfactants in small amounts. If the containers according to the invention are intended to enclose such agents, these agents preferably contain only certain nonionic surfactants, which are described below. Usually only weakly foaming nonionic surfactants are used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably in the 2-position methyl branch or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C _12- i ₄ alcohols containing 3 EO or 4 EO, _C9-11 alcohol containing 7 EO, C. ₁₃ ₁₅ alcohols with 3 EO, δ EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, δ EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ . ₁₄ -alcohol with 3 EO and C _12-18 -alcohol with δ EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In particular in the case of water-soluble containers according to the invention for the portioning, packaging and metering of detergents for machine dishwashing, it is preferred that they contain a nonionic surfactant which has a melting point above room temperature, preferably a nonionic surfactant with a melting point above 20 ° C. Nonionic surfactants to be used preferably have melting points above 2δ ° C, particularly preferred nonionic surfactants have melting points between 2δ and 60 ° C, in particular between 26.6 and 43.3 ° C.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) niol surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an elhoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms, (Cι. ₆ ₂₀ -alcohol), preferably a C ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 60% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants. Other nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight. -% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

Another preferred surfactant can be represented by the formula

R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (OH) R ² ]

describe in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0, δ and 1, 5 and y stands for a value of at least 1 δ.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and δ. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or - CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. If x stands for 3, for example, the radical R ³ can be selected to be ethylene oxide (R ³ = H) or To form propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO ), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

Preferred agents according to the invention, which are used as automatic dishwashing detergents, also contain amphoteric or cationic polymers in addition to the surfactants mentioned to improve the rinse aid result.

Agents produced according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents produced according to the invention preferably contain enzymes in total amounts of 1 × ^10'6 to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and that which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. The variants listed under the name BLAP ^{® are} derived from the protease from Bacillus lentus DSM 5483.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, which is sold under the trade name Protosol ^® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ^® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ^® and Protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens or from B. stearothermophilus and their further developments for use in detergents and cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α- amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase of B. amyloliquefaciens is sold by Novozymes under the name BAN ^®, and variants derived from the α- amylase ß. stearothermophilus under the names BSG ^® and Novamyl ^® , also from Novozymes.

Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9943); fusion products of the molecules mentioned can also be used.

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Another commercial product is the Amylase-LT ^® .

Agents produced according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to prepare suitable precursors To produce peracids. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^® , Lipolase ^® Ultra, LipoPrime ^® , Lipozyme ^® and Lipex ^® . Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^® and Lipase AML ^® available. For example, the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention, also the product Lumafast ^® from Genencor.

Agents produced according to the invention, especially if they are intended for the treatment of textiles, can contain celiulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects. To this

Performance aspects include, in particular, contributions to the primary washing performance, to the secondary washing performance of the agent (anti-deposition effect or graying inhibition) and avivage (tissue effect), to the exertion of a “slone washed” effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ^® . The products Endoiase ^® and Carezyme ^{®, which} are also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from H. insolens DSM 1600. Other possible commercial products from this company are Cellusoft ^® and Renozyme ^® . The 20 kD EG cellulase from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ^® and Biotouch ^® , can also be used. Other commercial products from AB Enzymes are Econase ^® and Ecopulp ^® . Another suitable cellulase from Bacillus sp. CBS 670.93 is available from Genencor under the trade name Puradax ^® . Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge ^® Neutra. Agents produced according to the invention can contain further enzymes, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , The from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, washing or cleaning agents according to the invention can use oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain. Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling.

The enzymes used in agents according to the invention either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.

The enzymes in question are advantageously purified by methods which are in themselves established, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

Agents according to the invention can be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed in a solidified gel or in those of the core-shell type in which an enzyme-containing core with a water, air and / or chemical-impermeable protective layer is coated. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

A protein and / or enzyme contained in an agent according to the invention can be protected, particularly during storage, against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Agents manufactured according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho, meta- or para-substituted phenylboronic acids, or their salts or esters. Peptide aldehydes, ie oligopeptides with a reduced C-terminus, are also suitable. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End group-capped fatty acid amide alkoxylates can also be used as stabilizers.

Lower aliphatic alcohols, but above all polyols, such as, for example, glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation by physical influences. Likewise Calcium salts are used, such as calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or, such as cellulose ethers, acrylic polymers and / or polyamides, stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can also stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.

Reducing agents and antioxidants such as sodium sulfite or reducing sugars increase the stability of the enzymes against oxidative breakdown.

Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The action of peptide-aldehyde stabilizers can be increased by the combination with boric acid and / or boric acid derivatives and polyols and can be further enhanced by the additional use of divalent cations, such as calcium ions.

The use of liquid enzyme formulations is particularly preferred in the context of the present invention. Agents produced according to the invention are preferred here, which additionally contain enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably of 1, 5 to 4, 5 and in particular from 2 to 4 wt .-%, each based on the total agent.

In order to facilitate the disintegration of the solids optionally included in the agents according to the invention, such as tablets or granules, these compresses can contain disintegration aids, so-called tablet disintegrants. Under

According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for the rapid disintegration of Tablets in water or gastric juice and ensure the release of the pharmaceuticals in an absorbable form. These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives. All of the disintegration aids mentioned can be used according to the invention.

In the context of the present invention, preferred disintegration aids are cellulose-based disintegration aids, preferably in granular, cogranulated or compacted form.

Pure cellulose has the formal gross composition (C ₆ Hιo0 ₅ ) n and formally considered a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

The cellulose derivatives mentioned are preferably not used alone as cellulose-based disintegration agents, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant. Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but the crystalline areas (approx. 70%) leave undamaged. Subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

In addition to or instead of the cellulose-based disintegration aids, the agents according to the invention can contain a gas-releasing system composed of organic acids and carbonates / hydrogen carbonates.

The solid mono-, oligo- and polycarboxylic acids, for example, can be used as organic acids which release carbon dioxide from the carbonates / bicarbonates in aqueous solution. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 60% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

The acids mentioned do not have to be used stoichiometrically to the carbonates or hydrogen carbonates contained in the compressed products.

A detergent and cleaning agent compact preferred in the context of the present invention additionally contains a shower system.

In the agents according to the invention, the gas-developing shower system consists of carbonates and / or bicarbonates in addition to the organic acids mentioned. For reasons of cost, the alkali metal salts are clearly preferred among representatives of this class of substances. In the case of the alkali metal carbonates or bicarbonates, in turn, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or hydrogen carbonates concerned do not have to be used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. Out From a manufacturing point of view, the use of NaCl or MgCl ₂ in the granules according to the invention is preferred.

In order to bring the pH of solutions of the water-soluble containers according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. Usually the amount of these adjusting agents does not exceed 1% by weight of the total formulation.

In the context of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallyl propalate and benzylate propionate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, cc-isomethylionon and methyl-cedrylketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The general description of the perfumes that can be used (see above) generally represents the different substance classes of fragrances. In order to be perceptible, a fragrance must be volatile, in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role plays. Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, the odor impressions being described as "top note", "heart or middle note" (middle note or body ) and "base note" (end note or dry out) divided. Since the smell is largely based on the intensity of the smell, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile, ie sticky odorants. When composing perfumes, more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly. In the subsequent classification of the fragrances into "more volatile" or "adherent" fragrances, nothing is said about the odor impression and whether the corresponding fragrance is perceived as a top or heart note.

The smell of the water-soluble containers according to the invention or the solids contained in them (product fragrance) and, after the cleaning and care process has ended, the laundry fragrance, for example, can also be influenced by a suitable selection of the fragrances or perfume oils mentioned. Due to their design, in particular due to the openings in the outer wall, water-soluble containers according to the invention are particularly suitable in comparison to completely sealed containers, in order to ensure an unmistakable product fragrance even when using smaller amounts of fragrance, whereby, in particular, more volatile fragrances can also be used, while To achieve a sufficient scent of laundry, the use of stronger odoriferous substances is advantageous. Tenacious odoriferous substances which are usable in the context of the present invention are, for example, essential oils such as angelica root oil, anise oil arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, silver fir oil noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, Fichlennandelöl, galbanum oil, geranium oil Ginger grass oil, guaiac wood oil, gurjun balsam oil , Helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil Kopaϊvabalsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemon oil, lemon oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil, lime oil Neroli oil, Niaouli oil, Olibanum oil, Orange oil, Origanum oil, Palmarosa oil, Patchouli oil, Peru balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Allspice oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Spik oil, Star anise oil, Turpentine oil, Thuja oil, Thuja oil, Thuja oil, Thuja oil, Thuja oil Vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil. However, the higher-boiling or solid odorants of natural or synthetic origin can also be used in the context of the present invention as adherent odorants or odorant mixtures, that is to say fragrances. These compounds include the compounds mentioned below and mixtures of these: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzyl benzate, boryl formate benzyl benzate, benzyl formate benzyl benzyl benzate, benzyl formate benzyl benzyl benzate, benzyl formate benzyl benzate, benzyl formate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl formate benzyl formate benzyl benzoate benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzoate , Bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, Farnesol, Fenchon, Fenchylacetate, Geranyl acetate, Geranyl formate, Heliotropin, Heptin carboxylic acid methyl ester, Heptaldehyde, Hydroquinone dimethyl ether, Hydroxycinnamaldehyde, Hydroxycinnam alcohol, Indole, Iran, Isoeugenol, Isoeugenol methyl ether, Isosferol, Karvol, Kromone, Karolmone, kampon, kolomone, kampol, kasol, kumarol, kasmol, kumarol, kasol, kumarol, kasol, kumarol, kasmol, kumarol, kasol, kumarol, kasol, kumarol, kasol, kumarol, kasmol, kumarol, kasmol, kasol, kumarol, kasol. Methoxyacetophenone, methyl-n-amylketone, methylanthranilic acid, methyl ester, p-methylacetophenone, methylchavikol, p-methylquinoline, methyl-ß-naphthylketone, methyl-n-nonylacetaldehyde, methyl-n-nonylketone, muskon, ß-naphthethyl etherol, nerol Nitrobenzene, n-nonylaldehyde, nony alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, ß-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegon, safrol, salicyl acidoloyl ester, methyl salicyl ester, salicyl acid methyl ester, Thymol, γ-undelactone, vanilin, veratrum aldehyde, cinnamaldehyde, cimate alcohol, cinnamic acid, Ethyl cinnamate, benzyl cinnamate. The more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the compositions and to light. If the containers of washing and cleaning waste according to the invention for textile cleaning enclose, the dyes used should furthermore have no pronounced substantivity towards textile fibers in order not to dye them.

Hydrotropes or solubilizers are substances that, through their presence, make other compounds that are practically insoluble in a certain solvent soluble or emulsifiable in this solvent (solubilization). There are solubilizers that form a molecular compound with the poorly soluble substance and those that work through micell formation. It can also be said that solubilizers only give a so-called latent solvent its solvency. When water is used as a (latent) solvent, one speaks mostly of hydrotropes instead of solubilizers, in some cases better of emulsifiers.

Foam inhibitors which can be used in the agents according to the invention include soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable carrier materials are, for example inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials. Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are structured according to the scheme (R ₂ SiO) x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with a molecular weight between 1000-160,000, and viscosities between 10 u. 1,000,000 mPa ^• s.

Suitable anti-redeposition agents, which are also referred to as soil repeilents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups from 1 δ to 30% by weight and of hydroxypropyl groups from 1 to 16% by weight, based in each case on the nonionic Cellulose ethers and the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or

Polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances absorb onto the fiber and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, wherein the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and produces the yellow shade of the grayed or yellowed laundry pure white. Suitable compounds originate for example from the substance classes of the 4,4 ^', 2,2'-stilbenedisulfonic -Diamino- ( flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems, and pyrene derivatives substituted by heterocycles.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Also usable as graying inhibitors are cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as

Methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

Since textile fabrics, in particular made from rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the grain are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkyl esters, aikylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters. A substance that is particularly suitable for textile finishing and care is cottonseed oil, which can be produced, for example, by pressing out the brown, cleaned cottonseed and refining it with about 10% sodium hydroxide or by extraction with hexane at 60-70 ° C. Such cotton oils contain 40 to δδ% by weight of linoleic acid, 16 to 26% by weight of oleic acid and 20 to 26% by weight of palmitic acid. Further agents which are particularly preferred for fiber smoothing and fiber care are the glycerides, in particular the monoglycerides of fatty acids such as, for example, glycerol monooleate or glycine monostearal.

To combat microorganisms, the agents according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between baklerioslatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely in the inventive agents.

In order to prevent undesirable changes in the washing and cleaning agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents according to the invention can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are usually substances with at least one hydrophilic Molecular ligands and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional finishing effect.

Phobing and impregnation processes are used to provide textiles with substances that prevent dirt from accumulating or make it easier to wash out. Preferred waterproofing and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. Antistatic agents can also be included. The dirt-repellent finish with phobing and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. Another area of application of waterproofing and impregnating agents is the water-repellent finishing of textile goods, tents, tarpaulins, leather, etc., which, in contrast to waterproofing, does not close the fabric pores, which means that the fabric remains breathable (hydrophobic). The hydrophobizing agents used for the hydrophobizing coat textiles, leather, paper, wood etc. with a very thin layer of hydrophobic groups, such as longer alkyl celts or siloxane groups. Suitable water repellents are e.g. B. paraffins, waxes, metal soaps, etc. with additives to aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, organotin compounds and glutardialdehyde and perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless - similar to greased substances - drops of water roll off them without wetting them. So z. B. silicone-impregnated textiles a soft handle u. are water u. stain-resistant; Stains from ink, wine, fruit juices and the like are easier to remove.

The non-aqueous solvents which can be used in the agents according to the invention include, in particular, the organic solvents, of which only the most important can be listed here: alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol) ), Ether and the like Glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ether), ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, glycol esters), amides and other nitrogen compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (Carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (nitrobenzene), halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, tri-, tetrachlorethylene, 1, 2-dichloroethane, chlorofluorocarbons), hydrocarbons (petrol, petroleum ether, cyclohexane, decalin -Solvent, benzene, toluene, xylenes). Alternatively, instead of the pure solvents, their mixtures, which for example advantageously combine the solution properties of different solvents, can also be used. Such a solvent mixture, which is particularly preferred in the context of the present application, is, for example, benzine, a mixture of various hydrocarbons suitable for chemical cleaning, preferably with a content of C12 to C14 hydrocarbons above 60% by weight, particularly preferably above 80% by weight and in particular above 90% by weight, based in each case on the total weight of the mixture, preferably with a boiling range from δ1 to 110 ° C.

The agents according to the invention can contain fabric softeners to care for the textiles and to improve the textile properties such as a softer "handle" (softening) and reduced electrostatic charging (increased wearing comfort). The active ingredients in fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic residues, such as for example the disteraryldimethylammonium chloride, which, however, because of its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation. Such "esterquats" with improved biodegradability can be obtained, for example, by mixing mixtures of methyldielhanolamine and / or triethanolamine esterified with fatty acids and the reaction products then quaternized with alkylating agents in a manner known per se. Dime is also suitable as a finish lhylolelhylenhamstoff.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are wholly or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which have, for example, polyethylene glycols and the polyalkylene oxide-modified dimethyl polysiloxanes. Because of their fiber-caring effect, protein hydrolyzates are further active substances preferred in the field of detergents and cleaning agents in the context of the present invention. Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins). According to the invention, protein hydrolyzates of both vegetable and animal origin can be used. Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolyzates, which can also be in the form of salts. According to the invention, the use of protein hydrolysates of plant origin, e.g. B. soy, almond, rice, pea, potato and wheat protein hydrolyzates. Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures or individual amino acids, such as arginine, lysine, histidine or pyrroglutamic acid, which have otherwise been obtained, can optionally be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products.

Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.

Detergents for automatic dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents and glass corrosion inhibitors in particular being particularly important in the field of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred are the Transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of the Cobalt or manganese and the manganese sulfate and the manganese complexes

[Me-TACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-TACN)] ²⁺ (PF ₆ ^_ ) ₂ >

[Me-MeTACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-MeTACN)] ²⁺ (PF ₆ ^" ) ₂ .

[Me-TACN) Mn ^lll (m-0) (m-0Ac) ₂ Mn ^lll (Me-TACN)] ²⁺ (PF ₆ -) ₂ and [Me-MeTACN) Mn ^lll (m-0) (m- 0Ac) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ ^" ) ₂ , where Me-TACN for 1, 4,7-trimethyl-1, 4J-triazacyclononane and Me-MeTACN for 1, 2,4,7 -tetramethyl-1, 4,7-triazacyclononane .. Zinc compounds can also be used to prevent corrosion on the wash ware.

In the context of the present invention, it is preferred to additionally select at least one silver protective agent from the group of the triazoles, the benzotriazoles, the bisbenzothazoles, the aminolriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1% by weight, preferably from 0.01 to 0.05% by weight and in particular from 0.06 to 0.25% by weight, in each case based on the total weight of the solids enclosed in the water-soluble containers according to the invention.

In addition to the above-mentioned silver protection agents, agents produced according to the invention can furthermore contain one or more substances for reducing glass corrosion. In the context of the present application, in particular additives of zinc and / or inorganic and / or organic zinc salts and / or silicates, for example the layered crystalline nathumdisilikal SKS 6 from Clariant GmbH, and / or water-soluble glasses, for example glasses which have a loss in mass of at least 0 , 5 mg under the conditions specified in DIN ISO 719, preferred to reduce glass corrosion. Particularly preferred agents contain at least one zinc salt of an organic acid, preferably selected from the group zinc oleate, zinc stearate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.

Another subject of the present application are deep-drawing dies with lowerable partial areas, preferably lowerable punches and / or lowerable webs.

Another object of the present application is the use of deep-drawing matrices with lowerable partial areas, preferably lowerable stamps and / or removable webs for the production of packaging for active substances or active substance mixtures. Suitable as active substances are in particular all active substances or active substance mixtures from the fields of pharmaceuticals, cosmetics, feed, crop protection or fertilizers, adhesives, foods and / or personal care products, but preferably from the field of detergent and cleaning substances.

Preferred active substances or active substance mixtures from the field of cosmetics are, in particular, hair setting agents, hair shaping agents and hair coloring agents. In addition to hair washing and hair care products, the preferred personal care products also include pre-treatment agents, hairdressing aids and course rinses. Active substances from the area of bath additives, such as bath salts or bath tablets, but also shower, foam or cream baths, are also preferred.

Washing and cleaning-active substances from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes _: disintegration aids, electrolytes, pH regulators, fragrances, perfume carriers, dyes _: hydrotropes, foam inhibitors, anti-redeposition agents, optical brighteners are particularly preferred

Graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, phobing and impregnating agents, swelling and anti-slip agents, non-aqueous solvents, fabric softeners, and UV hydrolyzers.

For a detailed description of these substances or subslance mixtures, reference is made to the explanations above in the text in order to avoid repetition.

Claims

claims

1. A method for producing a container, comprising the steps of: a) deep-drawing a first covering material into the deep-drawing trough of a die, forming at least one receiving chamber; b) lowering a part of the die and deep-drawing while enlarging at least one of the receiving chamber formed in step a) and / or forming at least one further receiving chamber.

2. The method according to claim 1, characterized in that at least one of the receiving chambers is filled before and / or after the lowering of part of the die.

3. The method according to any one of claims 1 or 2, characterized in that at least one of the filled or unfilled receiving chambers is sealed with a second covering material before lowering a part of the die.

4. The method according to any one of claims 1 to 3, characterized in that a web or punch located in the deep-drawing trough of the die and / or a part of the die at least partially surrounding the deep-drawing trough in step a) is lowered.

5. The method according to claim 4, characterized in that the web or stamp a maximum width between 0.5 and 50 mm, preferably between 0.6 and 40 mm, particularly preferably between 0.7 and 30 mm and in particular between 0.3 and has 20 mm.

6. The method according to any one of claims 4 or 5, characterized in that the web or stamp in step d) to less than 95%, preferably less than δ0%, particularly preferably to less than 65% and in particular less than 50% of its original Height is lowered.

7. The method according to any one of claims 1 to 6, characterized in that one of the shell materials used is water-soluble or water-dispersible.

δ. Method according to one of claims 1 to 7, characterized in that at least one of the envelope materials used is transparent or translucent.

9. The method according to any one of claims 1 to δ, characterized in that one of the shell materials used consists of a water-soluble or water-dispersible polymer, preferably a polymer film.

10. The method according to any one of claims 1 to 9, characterized in that the shell materials used consist of water-soluble or water-dispersible material and have different dissolution rates.

11. The method according to any one of claims 2 to 10, characterized in that at least one of the receiving chambers before and / or after lowering a part of the matrix is filled with at least one active substance or an active substance preparation, the release of which is delayed.

12. Deep-drawing dies with lowerable sections, preferably lowerable punches and / or lowerable webs.

13. Use of deep-drawing matrices with lowerable partial areas, preferably lowerable stamps and / or removable bars for the production of packaging for active substances or active substance mixtures.